The present invention relates to a composition comprising at least one 1,3,5-triazine derivative and also to its use in or for the manufacture of cosmetic or dermatological compositions for protecting the skin and/or the lips and/or integuments against ultraviolet radiation, in particular solar radiation.
It is known that light radiation with wavelengths of between 280 nm and 400 nm permits tanning of the human epidermis, and that light rays with wavelengths of between 280 nm and 320 nm, known as UV-B rays, cause skin burns and erythema which may be harmful to the development of a natural tan; this UV-B radiation should thus be screened out.
It is also known that UV-A rays, with wavelengths of between 320 nm and 400 nm, which cause tanning of the skin, are liable to induce an adverse change in the latter, especially in the case of sensitive skin or of skin which is continually exposed to solar radiation. UV-A rays cause in particular a loss of elasticity of the skin and the appearance of wrinkles, leading to premature skin aging. They promote triggering of the erythemal reaction or amplify this reaction in certain individuals and may even be the cause of phototoxic or photoallergic reactions. It is thus desirable also to screen out UV-A radiation.
Many cosmetic compositions intended for the photoprotection (UV-A and/or UV-B) of the skin have been proposed to date.
These anti-sun compositions are quite often in the form of an emulsion of oil-in-water type (that is to say a cosmetically acceptable vehicle consisting of a continuous aqueous dispersing phase and a discontinuous. 1,3,5-Triazine derivatives are particularly desired in anti-sun cosmetics due to the fact that they are highly active in the UV-B range, and even in the UV-A range for some of these compounds, depending on the nature of the substituents involved. Furthermore, they are photostable, i.e., they show little or no chemical degradation under the action of UV radiation. They are especially described in U.S. Pat. No. 4,617,390, EP 863 145, EP 517 104, EP 570 838, EP 796 851, EP 775 698, EP 878 469 and EP 933 376, and the following are known in particular:
2,4,6-tris[p-(2xe2x80x2-ethylhexyl-1xe2x80x2-oxycarbonyl) anilino]-1,3,5-triazine or xe2x80x9cEthylhexyl Triazonexe2x80x9d (INCI name), sold under the trade name xe2x80x9cUvinul T 150xe2x80x9d by BASF,
2-[(p-(tert-butylamido)anilino]-4,6-bis-[(p-(2xe2x80x2ethylhexyl-1xe2x80x2-oxycarbonyl)anilino]-1,3,5-triazine or xe2x80x9cDiethylhexyl Butamido Triazonexe2x80x9d (INCI name), sold under the trade name xe2x80x9cUvasorb HEBxe2x80x9d by Sigma 3V, and
2,4-bis{[4-2-ethylhexyloxy)]-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine or xe2x80x9cAnisotriazinexe2x80x9d (INCI name), sold under the trade name xe2x80x9cTinosorb Sxe2x80x9d by Ciba Specialty Chemicals.
It has been proposed in the prior art to use 1,3,5-triazine derivatives in oils such as esters and more particularly C12-C15 alkyl benzoates (xe2x80x9cFinsolv TNxe2x80x9d from Finetex), or triglycerides and especially C8-C12 fatty acid triglycerides (xe2x80x9cMiglyol 812xe2x80x9d from Hxc3xcls), or alternatively oxyethylenated or oxypropylenated fatty monoalcohols or polyols (xe2x80x9cCetiol HExe2x80x9d from Henkel or xe2x80x9cWitconol AMxe2x80x9d from Witco).
However, it has been observed that the photoprotective power of these triazine derivatives in the absence of other sunscreens is very limited and that their cosmetic properties are generally considered to be insufficient.
The problem posed underlying the present invention was that of improving the photoprotective efficacy of compositions containing such 1,3,5-triazine derivatives.
Surprisingly and unexpectedly, the inventors of the present patent application have shown that the use of at least one ester chosen from N-acyl amino acid esters of formula:
Rxe2x80x21(CO)N(Rxe2x80x22)CH(Rxe2x80x23)(CH2)n(CO)ORxe2x80x24
in which:
n is an integer equal to 0, 1 or 2,
Rxe2x80x21 represents a linear or branched C5 to C21 alkyl or alkenyl radical,
Rxe2x80x22 represents a hydrogen atom or a C1 to C3 alkyl group,
Rxe2x80x23 represents a radical chosen from the group formed by a hydrogen atom, a methyl group, an ethyl group and a linear or branched C3 or C4 alkyl chain, and
radical or a sterol residue, makes it possible to obtain a composition containing 1,3,5-triazine derivatives that have improved cosmetic and photoprotective properties. These N-acyl amino acid esters, and also the process for preparing them, are described in EP 1 044 676 and EP 0 928 608 to Ajinomoto Co.
The main advantage of these N-acyl amino acid esters is that they allow the production of anti-sun compositions containing 1,3,5-triazine derivatives and have a sun protection factor that is greater than that of the compositions of the prior art containing 1,3,5-triazine derivatives.
These compositions also have improved cosmetic qualities. They allow good moisturization of the skin, i.e., no drying of the skin is observed, nor, on the contrary, any excessively greasy feel.
One subject of the present invention is thus a composition containing at least one 1,3,5-triazine derivative and at least one ester chosen from N-acyl amino acid esters.
Another subject of the invention consists in using such a composition to manufacture cosmetic or dermatological compositions.
A subject of the invention is also a cosmetic treatment process comprising the application of a composition according to the present invention, and also the use of at least one N-acyl amino acid ester of formula:
Rxe2x80x21(CO)N(Rxe2x80x22)CH(Rxe2x80x23)(CH2)n(CO)ORxe2x80x24
in which:
n is an integer equal to 0, 1 or 2,
Rxe2x80x21 represents a linear or branched C5 to C21 alkyl or alkenyl radical,
Rxe2x80x22 represents a hydrogen atom or a C1 to C3 alkyl group,
Rxe2x80x23 represents a radical chosen from the group formed by a hydrogen atom, a methyl group, an ethyl group and a linear or branched C3 or C4 alkyl chain, and
Rxe2x80x24 represents a linear or branched C1 to C10 alkyl radical or a linear or branched C2 to C10 alkenyl radical or a sterol residue, in anti-sun compositions containing a 1,3,5-triazine derivative, in order to improve the sun protection factor of this composition.
Other subjects of the invention will become apparent on reading the description and the examples that follow.
The composition that is the subject of the invention preferably comprises, in a physiologically acceptable medium:
(i) at least one 1,3,5-triazine derivative, and
(ii) at least one ester chosen from N-acyl amino acid esters of formula:
Rxe2x80x21(CO)N(Rxe2x80x22)CH(Rxe2x80x23)(CH2)n(CO)ORxe2x80x24
xe2x80x83in which:
n is an integer equal to 0, 1 or 2,
Rxe2x80x21 represents a linear or branched C5 to C21 alkyl or alkenyl radical,
Rxe2x80x22 represents a hydrogen atom or a C1 to C3 alkyl group,
Rxe2x80x23represents a radical chosen from the group formed by a hydrogen atom, a methyl group, an ethyl group and a linear or branched C3 or C4 alkyl chain, and
Rxe2x80x24 represents a linear or branched C1 to C10 alkyl radical or a linear or branched C2 to C10 alkyl radical or a sterol residue.
In the formula for the amino acid esters presented above, the group Rxe2x80x21(CO)xe2x80x94 is an acyl group of an acid preferably chosen from the group formed by capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, linoleic acid, linolenic acid, oleic acid, isostearic acid, 2-ethylhexanoic acid, coconut oil fatty acids and palm kernel oil fatty acids. These fatty acids may also contain a hydroxyl group. Even more preferably, the fatty acid is lauric acid.
The portion xe2x80x94N(Rxe2x80x22)CH(Rxe2x80x23)(CH2)n(CO)xe2x80x94 of the amino acid ester is preferably chosen from the following amino acids: glycine, alanine, valine, leucine, isoleucine, serine, threonine, proline, hydroxyproline, xcex2-alanine, aminobutyric acid, aminocaproic acid, sarcosine and N-methyl-xcex2-alanine.
Even more preferably, the amino acid is sarcosine.
The portion of the amino acid esters corresponding to the group ORxe2x80x24 may be obtained from alcohols chosen from the group formed by methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, isobutanol, 3-methyl-1-butanol, 2-methyl-1-butanol, fusel oil, pentanol, hexanol, cyclohexanol, octanol, 2-ethylhexanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, cetostearyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, jojoba alcohol, 2-hexadecyl alcohol, 2-octyldodecyl alcohol and isostearyl alcohol.
These amino acid esters may be obtained in particular from natural sources of amino acids. In this case, the amino acids are obtained from the hydrolysis of natural proteins of plants (oat, wheat, soybean, palm or coconut) and then necessarily lead to mixtures of amino acids that will subsequently be esterified and then N-acylated. The preparation of such amino acids is more particularly described in FR 2 796 550, which is expressly incorporated herein by reference.
The amino acid ester that is more particularly preferred for use in the present invention is isopropyl N-lauroylsarcosinate of formula:
CH3xe2x80x94(CH2)10COxe2x80x94N(CH3)xe2x80x94CH2xe2x80x94COOxe2x80x94CH2xe2x80x94(CH3)2.
The 1,3,5-triazine derivative corresponds to formula (I) below: 
in which the radicals A1, A2 and A3, which may be identical or different, are chosen from the group of formulas (II) to (IX) below: 
in which:
Xa (each of the groups Xa may be identical or different) represents oxygen or xe2x80x94NHxe2x80x94;
Ra (each of the groups Ra may be identical or different) is chosen from hydrogen; an alkali metal; an ammonium radical optionally substituted with one or more linear or branched C1-C18 alkyl or linear or branched C1-C18 hydroxyalkyl radicals; a linear or branched C1-C18 and preferably C6-C12 alkyl radical; a C5-C12 cycloalkyl radical optionally substituted with one or more C1-C4 alkyl radicals; a polyoxyethylenated radical comprising from 1 to 6 ethylene oxide units, the terminal OH group of which is methylated; and a radical of formula (X), (XI) or (XII) below: 
in which:
R8 is hydrogen or a methyl radical;
R9 is a C1-C9 alkyl radical;
q is an integer equal to 0; 1; 2; 3;
r is an integer equal to 1; 2; 3; 4; 5; 6; 7; 8; 9; 10;
A is a C4-C8 alkyl radical or a C5-C8 cycloalkyl radical;
B is chosen from: a linear or branched C1-C8 alkyl radical;
a C5-C8 cycloalkyl radical; and an aryl radical optionally substituted with one or more C1-C4 alkyl radicals; and
R1 denotes a C3-C18 alkyl radical; a C2-C18 alkenyl radical; a residue of formula xe2x80x94CH2xe2x80x94CH(OH)xe2x80x94CH2xe2x80x94OT1 in which T1 is a hydrogen atom or a C1-C8 alkyl radical; or a residue of formula (XIII) below: 
in which:
R13 denotes a covalent bond; a linear or branched C1-C4 alkyl radical or a radical of formula xe2x80x94Cm1H2m1xe2x80x94 or xe2x80x94Cm1H2m1xe2x80x94Oxe2x80x94 in which m1 is an integer equal to 1; 2; 3; 4;
p1 is an integer equal to 0; 1; 2; 3; 4; 5;
the radicals R10, R11 and R12, which may be identical or different, denote a C1-C18 alkyl radical; a C1-C18 alkoxy radical or a radical of formula: 
in which R14 is a C1-C5 alkyl radical,
R2 denotes a hydrogen atom, a linear or branched C1-4 alkyl radical or a C1-C4 alkoxy radical;
R3 and R4, which may be identical or different, denote a linear or branched C1-C20 alkyl radical;
R5 represents a hydrogen atom or a phenyl radical optionally substituted with a halogen or with a C1-C4 alkyl radical or with a C1-C4 alkoxy radical;
R6 is a linear or branched C1-C8 alkyl radical or a C1-C3 alkoxy radical, it being understood that, in the latter case, two adjacent radicals R6 on the same aromatic nucleus can together form an alkylidenedioxy group in which the alkylidene group contains 1 or 2 carbon atoms, OH, NHCOCH3 or NH2,
R7 denotes a hydrogen atom, a C1-C10 alkyl radical, a radical of formula: xe2x80x94(CH2CHR5xe2x80x94O)n1R8 in which n1 is a number from 1 to 16, or a radical of structure xe2x80x94CH2xe2x80x94CHxe2x80x94(OH)xe2x80x94CH2OT1 with R8 and T1 having the same meaning as indicated above,
Z represents oxygen, sulphur, xe2x80x94NHxe2x80x94 or xe2x80x94NR3xe2x80x94 with R3 representing a linear or branched C1-C20 alkyl radical;
p is 0, 1, 2 or 3, and
A1 can also be a halogen, a radical xe2x80x94N(R3)2, the two radicals R3 together possibly forming a ring of 4 or 5 carbon atoms, or a group xe2x80x94OR3, R3 having the same definition as above.
A first family of 1,3,5-triazine derivatives that is more particularly preferred, and that is described especially in EP-A-0 517 104, is that of the 1,3,5-triazines corresponding to formula (I) in which A1, A2 and A3 are of formula (II) and have all of the following characteristics:
one of the groups Xa-Ra represents a radical xe2x80x94NHxe2x80x94Ra with Ra chosen from: a C5-C12 cycloalkyl radical optionally substituted with one or more C1-C4 alkyl radicals; a radical of formula (X), (XI) or (XII) above in which:
B is a C1-C4 alkyl radical;
R9 is a methyl radical;
the other two groups Xa-Ra represent a radical xe2x80x94Oxe2x80x94Ra with Ra, which may be identical or different, chosen from: hydrogen;
an alkali metal; an ammonium radical optionally substituted with one or more alkyl or hydroxyalkyl radicals; a linear or branched C1-C18 alkyl radical; a C5-C12 cycloalkyl radical optionally substituted with one or more C1-C4 alkyl radicals; a radical of formula (X), (XI) or (XII) above in which:
B is a C1-C4 alkyl radical; and
R9 is a methyl radical.
A second family of 1,3,5-triazine derivatives that is more particularly preferred, and that is described especially in EP-A-0 570 838, is that of the 1,3,5-triazines corresponding to formula (I) in which A1, A2 and A3 are of formula (II) and have all of the following characteristics:
one or two groups Xa-Ra represent a radical xe2x80x94NHxe2x80x94Ra, with Ra chosen from: a linear or branched C1-C18 alkyl radical; a C5-C12 cycloalkyl radical optionally substituted with one or more C1-C4 alkyl radicals; a radical of formula (X), (XI) or (XII) above in which:
B is a C1-C4 alkyl radical; and
R9 is a methyl radical;
the other or the other two group(s) Xa-Ra being a radical xe2x80x94Oxe2x80x94Ra with Ra, which may be identical or different, chosen from: hydrogen; an alkali metal; an ammonium radical optionally substituted with one or more alkyl or hydroxyalkyl radicals; a linear or branched C1-C18 alkyl radical; a C5-C12 cycloalkyl radical optionally substituted with one or more C1-C4 alkyl radicals; and a radical of formula (X), (XI) or (XII) above in which:
B is a C1-C4 alkyl radical; and
R9 is a methyl radical.
A 1,3,5-triazine of this second family that is particularly preferred is 2-[(p-(tert-butylamido)-anilino]-4,6-bis[(p-(2xe2x80x2-ethylhexyl-1xe2x80x2-oxycarbonyl)-anilino]-1,3,5-triazine or xe2x80x9cDiethylhexyl Butamido Triazonexe2x80x9d sold under the trade name xe2x80x9cUvasorb HEBxe2x80x9d by Sigma 3V and corresponding to the following formula: 
in which Rxe2x80x2 denotes a 2-ethylhexyl radical and R denotes a tert-butyl radical.
A third preferred family of compounds that may be used in the context of the present invention, and which is described especially in U.S. Pat. No. 4,724,137, is that of the 1,3,5-triazines corresponding to formula (I) in which A1, A2 and A3 are of formula (II) and have all of the following characteristics:
Xa are identical and represent oxygen; and
Ra, which may be identical or different, represent a C6-C12 alkyl radical or a polyoxyethylenated radical comprising from 1 to 6 ethylene oxide units and in which the terminal OH group is methylated.
A 1,3,5-triazine of this third family that is particularly preferred is 2,4,6-tris[p(2xe2x80x2-ethylhexyl-1xe2x80x2-oxycarbonyl)anilino]-1,3,5-triazine or xe2x80x9cEthylhexyl Triazonexe2x80x9d sold especially under the trade name xe2x80x9cUvinul T 150xe2x80x9d by BASF and which corresponds to the following formula: 
in which Rxe2x80x2 denotes a 2-ethylhexyl radical.
A fourth preferred family of compounds that may be used in the context of the present invention, and which is described especially in EP-A-0 775 698, is that of the 1,3,5-triazines corresponding to formula (I) in which A1 and A2 are of formula (III) and A3 is of formula (IX) and have all of the following characteristics: R1, which may be identical or different, denote a C3-C18 alkyl radical; a C2-C18 alkenyl radical or a residue of formula xe2x80x94CH2xe2x80x94CH(OH)xe2x80x94CH2xe2x80x94OT1 in which T1 is a hydrogen atom or a C1-C8 alkyl radical; and R7 denotes a hydrogen atom or a C1-C10 alkyl radical.
A 1,3,5-triazine of this fourth family that is particularly preferred is 2,4-bis{[4-2-ethylhexyloxy)]-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine or xe2x80x9cAnisotriazinexe2x80x9d sold under the trade name xe2x80x9cTinosorb Sxe2x80x9d by Ciba Specialty Chemicals, and corresponds to the following formula: 
in which Rxe2x80x2 denotes a 2-ethylhexyl radical.
A fifth preferred family of compounds that may be used in the context of the present invention, and which is described especially in EP 507 691, EP 507 692, EP 790 243 and EP 944 624, and the technical content of which is expressly incorporated herein by reference, is that of the 1,3,5-triazines corresponding to formula (I) in which A1, A2 and A3 are of formulae (VII) to (XI) mentioned above.
As examples of these compounds of the above formula that may be used, mention may be made of:
2,4,6-tris(diisobutyl4xe2x80x2-aminobenzalmalonate)-s-triazine,
2,4,6-tris(bis(2-ethylhexyl)4xe2x80x2-aminobenzalmalonate)-s-triazine,
2,4,6-tris(bis(2-ethylhexyl)4xe2x80x2-aminobenzalmalonate)-6-chloro-s-triazine,
2,4,6-tris(bis(2-ethylhexyl)4xe2x80x2-aminobenzalmalonate)-6-(2-ethylhexyl4xe2x80x2-aminobenzoate)-s-triazine,
2,4,6-tris(diisobutyl4xe2x80x2-aminobenzalmalonate)-6-butoxy-s-triazine,
2,4,6-tris(diisobutyl4xe2x80x2-aminobenzalmalonate)-6-(2-ethylhexylamino)-s-triazine,
2,4-bis(4xe2x80x2-aminobenzylidenecamphor)-6-(2-ethylhexylamino)-s-triazine,
2,4-bis(4xe2x80x2-aminobenzylidenecamphor)-6-(diisobutyl4xe2x80x2-aminobenzalmalonate)-s-triazine,
2,4,6-tris(diethyl 4xe2x80x2-aminobenzalmalonate)-s-triazine,
2,4,6-tris(diisopropyl4xe2x80x2-aminobenzalmalonate)-s-triazine,
2,4,6-tris(dimethyl 4xe2x80x2-aminobenzalmalonate)-s-triazine,
2,4,6-tris(ethylxcex1-cyano-4-aminocinnamate)-s-triazine,
2,4,6-tris[(3xe2x80x2-benzotriazol-2-yl-2xe2x80x2-hydroxy-5xe2x80x2-methyl)phenylamino]-s-triazine, and
2,4,6-tris[(3xe2x80x2-benzotriazol-2-yl-2xe2x80x2-hydroxy-5xe2x80x2-tert-octyl)phenylamino]-s-triazine.
A 1,3,5-triazine of this fifth family that is particularly preferred is 2,4,6-tris(diisobutyl 4xe2x80x2-aminobenzalmalonate)-s-triazine, which corresponds to the following formula: 
The compositions according to the present invention preferably comprise, in a physiologically acceptable medium, from 0.05% to 15%, and preferably from 0.1% to 10%, of 1,3,5-triazine derivatives by weight relative to the total weight of the composition.
The compositions according to the present invention preferably comprise, in a physiologically acceptable medium, from 0.1% to 50%, and preferably from 1% to 30%, of N-acyl amino acid esters by weight relative to the total weight of the composition.
The composition according to the present invention is preferably a cosmetic composition containing, besides the 1,3,5-triazine derivative as organic screening agent, at least one other additional UV-A-active and/or UV-B-active organic screening agent (absorber) that is water-soluble, liposoluble or insoluble in the cosmetic solvents commonly used.
These organic UV screening agents are chosen from dibenzoylmethane derivatives, cinnamic derivatives, anthranilates; salicylic derivatives; camphor derivatives; benzophenone derivatives; xcex2, xcex2-diphenylacrylate derivatives; benzotriazole derivatives; benzalmalonate derivatives; benzimidazole derivatives; imidazolines; bis-benzazolyl derivatives as described in EP 669 323 and U.S. Pat. No. 2,463,264; p-aminobenzoic acid (PABA) derivatives; methylenebis(hydroxyphenyl)benzotriazole derivatives as described in U.S. Pat. Nos. 5,237,071 and 5,166,355, GB 2 303 549, DE 197 26 184 and EP 893 119; screening polymers and screening silicones such as those described especially in WO 93/04665; dimers derived from xcex1-alkylstyrene, such as those described in DE 198 55 649, 4,4-diarylbutadienes such as those described in EP 0 967 200 and DE 197 55 649 (the disclosures of which are expressly incorporated herein by reference).
The para-benzoic acid derivatives that may be used in the compositions according to the present invention are as follows, and their INCI names are added in parentheses:
p-aminobenzoic acid (PABA),
2-ethyl-p-aminobenzoic acid (ethyl PABA)
(ethyl dihydroxypropyl PABA) sold under the name Amerscreen-P by Amerchol,
2-ethylhexyl p-dimethylaminobenzoate (ethylhexyl dimethyl PABA) sold especially under the trade name xe2x80x9cEscalol 507xe2x80x9d by ISP,
glyceryl p-aminobenzoate (glyceryl PABA),
ethoxylated (25 mol) p-aminobenzoate (PEG-25 PABA) sold under the trade name xe2x80x9cUvinul P25xe2x80x9d by BASF, and
N-propoxylated ethyl p-aminobenzoate.
The salicylic derivatives that may be used in the compositions according to the present invention are as follows, and their INCI names are added in parentheses:
homomenthyl salicylate (homosalate) sold under the trade name xe2x80x9cEusolex HMSxe2x80x9d by Rona/EM Industries,
2-ethylhexyl salicylate (ethylhexyl salicylate) sold under the trade name xe2x80x9cNeo Heliopan OSxe2x80x9d by Haarmann and Reimer,
(dipropylene glycol salicylate) sold under the trade name xe2x80x9cDipsalxe2x80x9d by Scher,
triethanolamine salicylate (TEA salicylate) sold under the trade name xe2x80x9cNeo Heliopan TSxe2x80x9d by Haarmann and Reimer, and
4-isopropylbenzyl salicylate.
The dibenzoylmethane derivatives that may be used in the compositions according to the present invention are as follows:
2-methyldibenzoylmethane,
4-methyldibenzoylmethane,
4-isopropyldibenzoylmethane,
4-tertbutyldibenzoylmethane,
2,4-dimethyldibenzoylmethane,
2,5-dimethyldibenzoylmethane,
4,4-diisopropyldibenzoylmethane,
4,4-dimethoxydibenzoylmethane,
4-tert-butyl-4xe2x80x2-methoxydibenzoylmethane,
2-methyl-5-isopropyl-4xe2x80x2-methoxydibenzoylmethane,
2-methyl-5-tert-butyl-4xe2x80x2-methoxydibenzoylmethane,
2,4-dimethyl-4xe2x80x2-methoxydibenzoylmethane, and
2,6-dimethyl-4-tert-butyl-4xe2x80x2-methoxydibenzoylmethane.
Among the dibenzoylmethane derivatives mentioned above, the one that is particularly preferred is 4-tert-butyl-4xe2x80x2-methoxydibenzoylmethane (butyl methoxydibenzoylmethane), sold especially under the trade name xe2x80x9cParsol(copyright) 1789xe2x80x9d by Hoffmann-Laroche.
Another dibenzoylmethane derivative that is preferred according to the present invention is 4-isopropyldibenzoylmethane (isopropyl dibenzoylmethane) sold under the name xe2x80x9cEusolex(copyright) 8020xe2x80x9d by Merck.
The cinnamic derivatives that may be used in the compositions according to the present invention are as follows:
2-ethylhexyl 4-methoxycinnamate (ethylhexyl methoxycinnamate) sold under the trade name xe2x80x9cParsol MCXxe2x80x9d by Hoffmann La Roche,
isopropyl methoxycinnamate,
isoamyl 4-methoxycinnamate (isoamyl methoxy cinnamate) sold under the trade name xe2x80x9cNeo Heliopan E 1000xe2x80x9d by Haarmann and Reimer,
cinoxate,
diethanolamine 4-methoxycinnamate (DEA methoxycinnamate),
methyl diisopropylcinnamate (diisopropyl methylcinnamate), and
(glyceryl ethylhexanoate dimethoxycinnamate).
The xcex2, xcex2xe2x80x2-diphenylacrylate derivatives that may be used in the compositions according to the present invention are as follows:
2-ethylhexyl 2-cyano-3,3-diphenylacrylate (octocrylene) sold under the trade name xe2x80x9cUvinul N539xe2x80x9d by BASF, and
2-ciano-3,3-diphenylacrylate (ethocrylene) sold under the trade name xe2x80x9cUvinul N35xe2x80x9d by BASF.
The benzophenonederivatesthat may be used in the compositions according to the present invention are as follows:
2,4-dihydroxybenzophenone (benzophenone-1), this product being sold under the name Uvinul(copyright) 400 by BASF;
2,2xe2x80x2,4,4xe2x80x2-tetrahydroxbenzophenone (benzophenone-2), this product being sold under the name Uvinul(copyright) D50 by BASF;
2-hydroxy-4-methoxybenzophenone, also known as oxybenzone (benzophenone-3), this procduct being sold under the name Uvinul(copyright) M40 by BASF;
2-hydroxy-4-methoxybenzophenone-5-sulphonic acid, also known as sulisobenzone (benzophenone-4), this product being sold under the name Uvinul(copyright) MS 40 by BASF; and also the sodium sulphonate form thereof (benzophenone-5);
2,2xe2x80x2-dihydroxy-4,4xe2x80x2-dimethoxybenzophenone (benzophenone-6), this product being sold under the name Heliosorb(copyright) 11 by Norquay;
5-chloro-2-hydroxybenone (benzophenone-13);
2,2xe2x80x2-dihydroxy-4-methoxybenzophenone, also known as dioxybenzone or benzophenone-8, this product being sold under the name Spectra-Sorb(copyright) UV-24 by American Cyanamid;
the disodium salt of 2,2xe2x80x2-dihydroxy-4,4xe2x80x2-di-methoxybenzophenone-5,5xe2x80x2-disulphonic acid (benzophenone-9), this product being sold under the name Uvinul(copyright) DS49 by BASF;
2-hydroxy-4-methoxy-4xe2x80x2-methylbenzophenone (benzophenone-7); and
2-hydroxy-4-(octyloxy)benzophenone (benzophenone-12).
The benzylidenecamphor derivatives that may be used in the compositions according to the present invention are as follows:
3-benzylidene-d,1-camphor (3-benzylidene camphor) manufactured under the trade name xe2x80x9cMexoryl SDxe2x80x9d by Chimex,
3-(4xe2x80x2-methylbenzylidene)-d,1-camphor (4-methylbenzylidene camphor) sold under the trade name xe2x80x9cEusolex 6300xe2x80x9d by Merck,
(benzylidene camphor sulfonic acid) manufactured under the trade name xe2x80x9cMexoryl SLxe2x80x9d by Chimex,
(camphor benzalkonium methosulfate) manufactured under the trade name xe2x80x9cMexoryl SOxe2x80x9d by Chimex,
(terephtalylidene dicamphor sulfonic acid) manufactured under the trade name xe2x80x9cMexoryl SXxe2x80x9d by Chimex,
(polyacrylamidomethyl benzylidene camphor) manufactured under the trade name xe2x80x9cMexoryl SWxe2x80x9d by Chimex.
The benzimidazole derivatives that may be used in the compositions according to the present invention are as follows:
2-phenylbenzimidazolyl-5-sulphonic acid sold under the trade name xe2x80x9cEusolex 232xe2x80x9d by Merck,
benzimidazilate sold under the trade name xe2x80x9cNeo Heliopan APxe2x80x9d by Haarmann and Reimer.
The benzotriazole derivatives that may be used in the compositions according to the present invention are as follows:
drometrizole trisiloxane sold under the name xe2x80x9cSilatrizolexe2x80x9d by Rhodia Chimie, and
methylenebis(benzotriazolyl)tetramethylbutylphenol, sold in solid form under the trade name xe2x80x9cMixxim BB/100xe2x80x9d by Fairmount Chemical, or in micronized form as an aqueous dispersion under the trade name xe2x80x9cTinosorb Mxe2x80x9d by Ciba Specialty Chemicals.
Among the anthranilates that may be used according to the present invention, mention may be made most particularly of menthyl anthranilate, sold under the trade name xe2x80x9cNeo Heliopan MA(copyright)xe2x80x9d by Haarmann and Reimer.
Among the imidazoline derivatives that may be used according to the present invention, mention may be made most particularly of ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate.
Among the benzalmalonate derivatives that may be used according to the present invention, mention may be made of polyorganosiloxanes containing a benzalmalonate function, such as the product sold under the trade name xe2x80x9cParsol SLXxe2x80x9d by Hoffmann Laroche.
The organic UV screening agents that are preferred for the purposes of the present invention are chosen from the following compounds:
ethylhexyl salicylate,
octocrylene,
phenylbenzimidazole sulfonic acid,
4-methylbenzylidene camphor,
benzimidazilate,
terephthalylidene dicamphor sulfonic,
benzophenone-3,
benzophenone-4,
benzophenone-5,
methylene bis-benzotriazolyl tetramethylbutylphenol,
drometrizole trisiloxane
and mixtures thereof.
The composition may also comprise nacres, pigments or nanopigments (average size of the primary particles: generally between 5 nm and 100 nm and preferably between 10 nm and 50 nm) of coated or uncoated metal oxides, such as, for example, nanopigments of titanium oxide (amorphous or crystallized in rutile and/or anatase form), of iron oxide, of zinc oxide, of zirconium oxide or of cerium oxide, and mixtures thereof, which are all UV photoprotective agents that are well known per se. Standard coating agents are, moreover, alumina and/or aluminium stearate. Such coated or uncoated metal oxide nanopigments are described in particular in EP-A-0 518 772 and EP-A-0 518 773.
The compositions of the invention may also comprise standard cosmetic adjuvants chosen especially from fatty substances, organic solvents other than those used specifically in the context of the present invention, emulsifiers, ionic or nonionic thickeners, softeners, antioxidants, free-radical scavengers, opacifiers, stabilizers, emollients, silicones, xcex1-hydroxy acids, antifoams, moisturizers, vitamins, insect repellants, fragrances, preserving agents, surfactants, anti-inflammatories, substance P antagonists, fillers, polymers, propellants, acidifying or basifying agents, colorants or any other ingredient usually used in cosmetics, in particular for the manufacture of anti-sun compositions in the form of emulsions.
The fatty substances may consist of an oil or a wax or mixtures thereof, and they also comprise fatty acids, fatty alcohols and fatty acid esters. The oils may be chosen from animal, plant, mineral and synthetic oils, and especially from liquid petroleum jelly, liquid paraffin, volatile or non-volatile silicone oils, isoparaffins, polyolefins, fluoro oils, perfluoro oils, and alkyl derivatives of benzoic acid and of hydrobenzoic acid. Similarly, the waxes may be chosen from animal, fossil, plant, mineral and synthetic waxes that are known per se.
Among the organic solvents that may be mentioned are lower alcohols and polyols.
Needless to say, a person skilled in the art will take care to select this or these optional additional compound(s) and/or the amounts thereof such that the advantageous properties, in particular the increase of the protection factor of the 1,3,5-triazine derivatives in the N-acyl amino acid ester, are not, or are not substantially, adversely affected by the envisaged addition(s).
The compositions of the invention may be prepared according to techniques that are well known to those skilled in the art, in particular those intended for preparing emulsions of oil-in-water (O/W) or water-in-oil (W/O) type.
These compositions may be in particular in the form of a simple emulsion or a complex emulsion: double (O/W or W/O) or triple (W/O/W or O/W/O) emulsion, such as a cream, a milk, a gel or a cream-gel; a powder or a solid tube, and may optionally be packaged as an aerosol and may be in the form of a mousse or spray.
When it is an emulsion, the aqueous phase of this emulsion may comprise a nonionic vesicular dispersion prepared according to known processes (Bangham, Standish and Watkins, J. Mol. Biol. 13, 238 (1965), FR 2 315 991 and FR 2 416 008).
The cosmetic composition of the invention may be used as a composition for protecting the human epidermis or the hair against ultraviolet rays, as an anti-sun composition or as a makeup product.
When the cosmetic composition according to the invention is used for protecting the human epidermis against UV rays, or as an anti-sun composition, it may be in the form of a suspension or a dispersion in solvents or fatty substances, in the form of a nonionic vesicular dispersion or in the form of an emulsion, preferably of oil-in-water type, such as a milk or a cream, or in the form of an ointment, a gel, a cream-gel, a solid tube, a powder, a stick, an aerosol mousse or a spray.
When the cosmetic composition according to the invention is used for protecting the hair against UV rays, it may be in the form of a shampoo, a lotion, a gel, an emulsion or a nonionic vesicular dispersion and may constitute, for example, a rinse-out composition, to be applied before or after shampooing, before or after dyeing or bleaching, or before, during or after permanent-waving or straightening the hair, a styling or treating lotion or gel, a blow-drying or hairsetting lotion or gel, or a permanent-waving, straightening, dyeing or bleaching composition for the hair.
When the composition is used as a makeup product for the nails, the eyelashes, the eyebrows or the skin, such as an epidermal treatment cream, a foundation, a tube of lipstick, an eyeshadow, a face powder, mascara or an eyeliner, it may be in solid, pasty, anhydrous or aqueous form, for instance oil-in-water or water-in-oil emulsions, nonionic vesicular dispersions or suspensions.
As a guide, for the anti-sun formulations in accordance with the invention that contain a support of oil-in-water emulsion type, the aqueous phase (especially comprising the hydrophilic screening agents) generally represents from 50% to 95% by weight, and preferably from 70% to 90% by weight, relative to the total weight of the formulation, the oily phase (especially comprising the lipophilic screening agents) from 5% to 50% by weight, and preferably from 10% to 30% by weight, relative to the total weight of the formulation, and the (co)emulsifier(s) from 0.5% to 20% by weight, and preferably from 2% to 10% by weight, relative to the total weight of the formulation.
The present invention also relates to the use of a composition according to the present invention in or for the manufacture of cosmetic or dermatological compositions for protecting the skin and/or the lips and/or integuments (eyelashes, eyebrows, hair and nails) against ultraviolet radiation, in particular solar radiation, and also to a cosmetic treatment process, characterized in that it consists in applying a composition according to the present invention to the skin, the lips or integuments.